WO2021079977A1 - Polymère contenant un cycle triazine et composition filmogène le contenant - Google Patents

Polymère contenant un cycle triazine et composition filmogène le contenant Download PDF

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WO2021079977A1
WO2021079977A1 PCT/JP2020/039866 JP2020039866W WO2021079977A1 WO 2021079977 A1 WO2021079977 A1 WO 2021079977A1 JP 2020039866 W JP2020039866 W JP 2020039866W WO 2021079977 A1 WO2021079977 A1 WO 2021079977A1
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group
triazine ring
formula
containing polymer
carbon atoms
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PCT/JP2020/039866
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English (en)
Japanese (ja)
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直樹 中家
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日産化学株式会社
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Priority to US17/770,373 priority Critical patent/US20230002555A1/en
Priority to KR1020227016366A priority patent/KR20220095196A/ko
Priority to EP20878509.7A priority patent/EP4050049A4/fr
Priority to CN202080074297.XA priority patent/CN114599704A/zh
Priority to JP2021553554A priority patent/JPWO2021079977A1/ja
Publication of WO2021079977A1 publication Critical patent/WO2021079977A1/fr

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Definitions

  • the present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same.
  • liquid crystal displays organic electroluminescence (EL) elements (organic EL displays and organic EL lighting), touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors
  • EL organic electroluminescence
  • LED optical semiconductor
  • solid-state imaging elements organic thin-film solar cells
  • dye-sensitized solar cells dye-sensitized solar cells
  • organic thin-film transistors organic thin-film transistors
  • a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that low volume shrinkage can be achieved and that it is suitable as a film-forming composition for producing electronic devices (Patent Document 1).
  • the present invention has been made in view of the above circumstances, and can form a thin film having a high refractive index and excellent transparency and solvent resistance (crack resistance), as well as a low polar solvent, a hydrophobic solvent, and a low boiling point.
  • An object of the present invention is to provide a triazine ring-containing polymer having excellent solubility in various organic solvents such as a solvent, and a film-forming composition containing the same.
  • the present inventor has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group. It has been found that by using a triazine ring-containing polymer, a thin film having a high refractive index and excellent transparency and solvent resistance can be formed, and a triazine ring-containing polymer having excellent solubility in various organic solvents can be obtained. , The present invention has been completed.
  • the present invention provides the following triazine ring-containing polymer and a film-forming composition containing the same. [1]. It contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group.
  • a characteristic triazine ring-containing polymer ⁇ In the formula, R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
  • Ar represents at least one selected from the group represented by the formulas (2) to (13).
  • R 1 to R 92 are independent of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or a carbon.
  • R 93 and R 94 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • W 1 and W 2 are independent of each other and single bond, CR 95 R 96 (R 95 and R 96 are independent of each other and are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (however, they are together).
  • R 97 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or Represents a phenyl group.
  • X 1 and X 2 are independent of each other and have a single bond, an alkylene group having 1 to 10 carbon atoms, or the formula (14).
  • R 98 to R 101 are independent of each other, hydrogen atom, halogen atom, carboxyl group, sulfo group, alkyl group having 1 to 10 carbon atoms, alkyl halide group having 1 to 10 carbon atoms, or carbon. Represents an alkoxy group of numbers 1 to 10.
  • Y 1 and Y 2 independently represent a single bond or an alkylene group having 1 to 10 carbon atoms.
  • ) Represents a group. ] [2].
  • the triazine ring-containing polymer of the formula (15) whose arylamino group has a crosslinking group is the triazine ring-containing polymer of the formula (1) or [2]. (In the formula, R 102 represents a cross-linking group.) [4].
  • a 1 represents an alkylene group having 1 to 10 carbon atoms
  • a 2 is a single bond or the following formula (j).
  • a 3 represents a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group
  • a 4 represents a hydrogen atom or a methyl group, and a is 1 Or 2, it represents 2, and * represents a bond.
  • the cross-linking group is represented by a hydroxymethyl group, a 2-hydroxyethyl group, a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, and the following formulas (i-2) to (i-5).
  • a film-forming composition containing the triazine ring-containing polymer according to any one of [1] to [12] and an organic solvent [14].
  • the film-forming composition of [13], wherein the organic solvent contains at least one selected from a glycol ester solvent, a ketone solvent, and an ester solvent.
  • An electronic device comprising a base material and a thin film of [17] formed on the base material.
  • An optical member including a base material and a thin film of [17] formed on the base material.
  • a thin film having a high refractive index and excellent transparency and solvent resistance can be formed, and triazine having excellent solubility in various organic solvents such as a low polar solvent, a hydrophobic solvent and a low boiling solvent.
  • a ring-containing polymer can be provided.
  • a composition can be prepared using an organic solvent having a low dissolving power such as a low polar solvent and a hydrophobic solvent, so that the group is easily eroded by a high polar solvent.
  • a thin film can be formed on the material without any problem.
  • the thin film transistor produced from the film-forming composition of the present invention can exhibit the characteristics of high heat resistance, high refractive index, low volume shrinkage, and solvent resistance (crack resistance).
  • the thin film produced from the film-forming composition of the present invention has high transparency and high refractive index and solvent resistance (crack resistance), so that it is used as a flattening layer or a light scattering layer for organic EL lighting.
  • the light extraction efficiency (light diffusion efficiency) can be improved, and the durability can be improved.
  • FIG. 5 is a 1 H-NMR spectrum diagram of Compound P-5 (Polymer Compound [9]) obtained in Comparative Example 1-2. It is 1 H-NMR spectrum figure of the compound P-6 (polymer compound [10]) obtained in Example 1-4.
  • Example 3 is a 1 H-NMR spectrum diagram of Compound P-13 (Polymer Compound [19]) obtained in Comparative Example 3-1. It is an optical micrograph which observed the surface of the cured film obtained in Example 3-1. It is an optical micrograph which observed the surface of the cured film obtained in Comparative Example 3-1. It is 1 H-NMR spectrum figure of the compound P-22 (polymer compound [104]) obtained in Example 5-2. 6 is an optical micrograph of the cured film obtained in Example 6-1 after being exposed to a solvent. 6 is an optical micrograph of the cured film obtained in Example 6-2 after being exposed to a solvent.
  • the triazine ring-containing polymer according to the present invention contains a repeating unit structure represented by the following formula (1).
  • the triazine ring-containing polymer is, for example, a so-called hyperbranched polymer.
  • the hyperbranched polymer is a highly branched polymer having an irregular branched structure. Irregularity here means that it is more irregular than the branched structure of the dendrimer, which is a highly branched polymer having a regular branched structure.
  • the triazine ring-containing polymer which is a hyperbranched polymer, has a structure larger than the repeating unit structure represented by the formula (1), and has each of the three bonds of the repeating unit structure represented by the formula (1).
  • the structure A is distributed throughout except for the terminal of the triazine ring-containing polymer.
  • the repeating unit structure may be essentially composed only of the repeating unit structure represented by the formula (1).
  • R and R' represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other, but both may be hydrogen atoms from the viewpoint of further increasing the refractive index. preferable.
  • the carbon number of the alkyl group is not particularly limited, but 1 to 20 is preferable, and considering that the heat resistance of the polymer is further enhanced, the carbon number of the alkyl group is 1 to 10. More preferably, 1 to 3 is even more preferable.
  • the structure of the alkyl group is not particularly limited, and may be, for example, chain-like, branched, cyclic, or any combination of two or more thereof.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl.
  • N-pentyl 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-Dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl -N-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 1,
  • the carbon number of the alkoxy group is not particularly limited, but 1 to 20 is preferable, and 1 to 10 is more preferable as the carbon number of the alkoxy group in consideration of further enhancing the heat resistance of the polymer. 1 to 3 are even more preferable.
  • the structure of the alkyl moiety is not particularly limited, and may be, for example, chain-like, branched, cyclic, or any combination of two or more thereof.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n.
  • the carbon number of the aryl group is not particularly limited, but 6 to 40 is preferable, and 6 to 16 is more preferable as the carbon number of the aryl group in consideration of further enhancing the heat resistance of the polymer. 6 to 13 are even more preferable.
  • the aryl group includes an aryl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and the like.
  • aryl group examples include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, and the like.
  • p-Cyanophenyl ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenyl trill, 9-phenyl group and the like can be mentioned.
  • the number of carbon atoms of the aralkyl group is not particularly limited, but the number of carbon atoms is preferably 7 to 20, and the structure of the alkyl moiety thereof is not particularly limited. Any combination of In the present invention, the aralkyl group includes an aralkyl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and the like.
  • the above Ar represents at least one selected from the group represented by the formulas (2) to (13).
  • R 1 to R 92 are independent of each other, such as a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
  • R 93 and R 94 represent hydrogen atoms or alkyl groups with 1 to 10 carbon atoms
  • W 1 and W 2 are independent of each other, single bond, CR 95 R 96 (R 95).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group and the alkoxy group examples include the same as the alkyl group and the alkoxy group in R and R'.
  • the alkyl halide group having 1 to 10 carbon atoms is obtained by substituting at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms with a halogen atom, and specific examples thereof include trifluoromethyl. , 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl , 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,5,4-pentafluorobutyl, 2,2 , 3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,5,5,5-nonafluoropentyl, 2,2,3,3,4 , 4,5,5-octafluoropenty
  • a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, and a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable, in consideration of increasing the solubility of the triazine ring-containing polymer in a low polar solvent or the like while maintaining the refractive index.
  • Perfluoroalkyl groups are more preferred, and trifluoromethyl groups are even more preferred.
  • X 1 and X 2 independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14).
  • the structures of these alkyl groups, alkyl halide groups, alkoxy groups, and alkylene groups are not particularly limited, and may be, for example, chain-like, branched, cyclic, or any combination of two or more thereof.
  • the R 98 to R 101 are independent of each other and have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
  • Representing 10 alkoxy groups, Y 1 and Y 2 represent a single bond or an alkylene group having 1 to 10 carbon atoms independently of each other.
  • halogen atoms, alkyl groups, alkyl halide groups, and alkoxy groups include those similar to the halogen atoms, alkyl groups, alkyl halide groups, and alkoxy groups in R 1 to R 92.
  • alkylene group having 1 to 10 carbon atoms examples include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene group.
  • the structure of the alkylene group is not particularly limited, and may be, for example, chain-like, branched, cyclic, or any combination of two or more thereof.
  • R 1 to R 92 and R 98 to R 101 include a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, or a carbon number of carbon atoms.
  • Alkoxy groups of 1 to 5 are preferable, and hydrogen atoms are more preferable.
  • the triazine ring-containing polymer of the present invention preferably contains at least one halogen atom or an alkyl halide group having 1 to 10 carbon atoms in at least one aromatic ring among the aromatic rings contained in Ar. ..
  • the refractive index tends to decrease by introducing a fluorine atom into a compound, but the triazine ring-containing polymer of the present invention also has a fluorine atom introduced. Nevertheless, it maintains a refractive index of over 1.7.
  • the number of halogen atoms or alkyl halide groups in the aromatic ring can be any number that can be substituted on the aromatic ring, but considering the balance between the maintenance of the refractive index and the solubility in a solvent, 1 to 1 to Four is preferable, one or two is more preferable, and one is even more preferable.
  • the aromatic ring is a fused ring of a plurality of aromatic rings such as a naphthalene ring, it suffices to have at least one of the above groups as a whole.
  • Ar contains a plurality of aromatic rings
  • at least one aromatic ring contains at least one halogen atom or an alkyl halide group
  • all the aromatic rings contain a halogen atom or an alkyl halide group. It is preferable that all aromatic rings contain at least one halogen atom or an alkyl halide group.
  • At least one type represented by the formulas (2), (5) to (13) is preferable, and the formulas (2), (5), (7), (8), (11) to (13) are preferable. ) Is more preferable.
  • Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulas.
  • Ph represents a phenyl group
  • A represents a halogen atom or an alkyl halide group having 1 to 10 carbon atoms independently of each other, p is an integer of 0 to 4 independently of each other, and q is independent of each other.
  • An integer of 0 to 3 r is an integer of 0 to 2, independent of each other, s is an integer of 0 to 5, t is an integer of 1 to 6, and u is an integer of 1 to 4.
  • the sum of p, q, r, and s is 1 or more.
  • “Ph” represents a phenyl group.
  • the aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
  • Ph represents a phenyl group
  • the m-phenylene group represented by the formula (17) is preferable as Ar.
  • Ar is preferably a group having a diphenyl ether skeleton represented by the formulas (18) to (20).
  • the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group.
  • the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and the triazine ring at this terminal usually has two halogen atoms that can be substituted with the above-mentioned arylamino group having a cross-linking group. ing.
  • the arylamino group having the above-mentioned cross-linking group may be bonded to the same triazine ring terminal, or when there are a plurality of triazine ring terminals, each may be bonded to another triazine ring terminal. ..
  • Examples of the aryl group of the arylamino group having a crosslinking group include the same as above, but a phenyl group is particularly preferable.
  • the cross-linking group is bonded to an aryl group.
  • cross-linking group examples include a hydroxy-containing group, a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxy-containing group, a sulfo-containing group, a thiol-containing group, a (meth) acryloyl-containing group, and the like.
  • a hydroxy-containing group and a (meth) acryloyl-containing group are preferable in consideration of improving the heat resistance of the coalescence and the solvent resistance (crack resistance) of the obtained thin film.
  • hydroxy-containing group examples include a hydroxy group and a hydroxyalkyl group, but a hydroxyalkyl group having 1 to 10 carbon atoms is preferable, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, and a hydroxy having 1 to 3 carbon atoms is more preferable. Alkyl groups are even more preferred. Hydroxyalkyl groups having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, and the like.
  • the carbon atom to which the hydroxy group is bonded is a primary carbon atom, and among them, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable.
  • a hydroxyalkyl group having 1 to 3 carbon atoms is even more preferable, a hydroxymethyl group and a 2-hydroxyethyl group are even more preferable, and a 2-hydroxyethyl group is most preferable.
  • Examples of the (meth) acryloyl-containing group include a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, and a group represented by the following formula (i), which have an alkylene group having 1 to 10 carbon atoms (meth).
  • Meta) Acryloyloxyalkyl groups and groups represented by the following formula (i) are preferable, and groups represented by the following formula (i) are more preferable.
  • a 1 represents an alkylene group having 1 to 10 carbon atoms
  • a 2 is a single bond or the following formula (j).
  • a 3 represents a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group
  • a 4 represents a hydrogen atom or a methyl group, and a is 1 Or 2, it represents 2, and * represents a bond.
  • alkylene group contained in the (meth) acryloyloxyalkyl group having an alkylene group (alkanediyl group) having 1 to 10 carbon atoms examples include methylene, ethylene, trimethylene, propane-1,2-diyl, tetramethylene and butane-1. , 3-Diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decimethylene groups and the like.
  • those having an alkylene group having 1 to 5 carbon atoms are preferable, those having an alkylene group having 1 to 3 carbon atoms are preferable, and those having 1 to 3 carbon atoms are preferable.
  • those having 2 alkylene groups are more preferable.
  • (meth) acryloyloxyalkyl group examples include, for example, (meth) acryloyloxymethyl group, 2- (meth) acryloyloxyethyl group, 3- (meth) acryloyloxypropyl group, and 4- (meth) acryloyl.
  • Oxybutyl group is mentioned.
  • a 1 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group and an ethylene group.
  • alkylene group having 1 to 10 carbon atoms include those similar to the alkylene group contained in the above-mentioned (meth) acryloyloxyalkyl group.
  • a 2 represents a single bond or a group represented by the formula (j), and a group represented by the formula (j) is preferable.
  • a 3 is a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group. Specific examples thereof include an alkylene group having 1 to 5 carbon atoms and the following formula (k-1). ) ⁇ (k-3) (In the formula, * is the same as above.) Examples thereof include groups represented by, preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and further preferably a methylene group and an ethylene group. Examples of the alkylene group of A 3 include alkylene groups having 1 to 5 carbon atoms among the alkylene groups exemplified in A 1.
  • A represents 1 or 2, but 1 is preferable.
  • Preferable embodiments of the group represented by the formula (i) include those represented by the following formula (i-1).
  • More preferable embodiments of the group represented by the formula (i) include those represented by the following formulas (i-2) to (i-5).
  • Examples of the vinyl-containing group include an alkenyl group having a vinyl group at the terminal and having 2 to 10 carbon atoms. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl group and the like.
  • epoxy-containing group examples include epoxy, glycidyl, glycidyloxy group and the like. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, 4-glycidylbutyl group and the like.
  • oxetane-containing group examples include oxetane-3-yl, (oxetane-3-yl) methyl, 2- (oxetane-3-yl) ethyl, 3- (oxetane-3-yl) propyl, and 4- (oxetane-3-yl).
  • oxetane-3-yl examples include oxetane-3-yl, (oxetane-3-yl) methyl, 2- (oxetane-3-yl) ethyl, 3- (oxetane-3-yl) propyl, and 4- (oxetane-3-yl).
  • Butyl group and the like can be mentioned.
  • Examples of the carboxy-containing group include a carboxy group and a carboxyalkyl group having 2 to 10 carbon atoms.
  • the carbon atom to which the carboxy group is bonded is preferably a primary carbon atom, and specific examples thereof include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and 4-. Examples include a carboxybutyl group.
  • the sulfo-containing group examples include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms.
  • the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples thereof include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl groups. And so on.
  • the thiol-containing group examples include a thiol group and a mercaptoalkyl group having 1 to 10 carbon atoms.
  • the carbon atom to which the thiol group is bonded is preferably a primary carbon atom, and specific examples thereof include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl and 4-. Examples include a mercaptobutyl group.
  • the number of cross-linking groups in the arylamino group having the above-mentioned cross-linking group is not particularly limited and may be any number substitutable on the aryl group, but the balance between solvent resistance and solubility in a solvent can be used. In consideration of, 1 to 4 is preferable, 1 to 2 is more preferable, and 1 is even more preferable.
  • Examples of the arylamino group having a suitable cross-linking group include those represented by the formula (15), and in particular, those represented by the formula (16) having a cross-linking group at the para position with respect to the amino group are preferable.
  • R 102 represents a cross-linking group.
  • R 102 has the same meaning as above.
  • arylamino group having a cross-linking group examples include those represented by the following formulas, but are not limited thereto.
  • the arylamino group having a hydroxyalkyl group can be introduced by using the corresponding hydroxyalkyl group-substituted arylamino compound in the production method described later.
  • Specific examples of the hydroxyalkyl group-substituted arylamino compound include (4-aminophenyl) methanol and 2- (4-aminophenyl) ethanol.
  • the arylamino group having a (meth) acryloyloxyalkyl group can be obtained by a method using a corresponding (meth) acryloyloxyalkyl group-substituted arylamino compound or after introducing an arylamino group having a hydroxyalkyl group into a triazine ring-containing polymer. Further, it can be introduced by a method in which (meth) acrylate halide or glycidyl (meth) acrylate is allowed to act on the hydroxy group contained in the hydroxyalkyl group.
  • the arylamino group having a group represented by the formula (i) can be prepared by a method using an arylamino compound having a desired cross-linking group or by introducing an arylamino group having a hydroxyalkyl group into a triazine ring-containing polymer. Further, it can be introduced by a method in which a (meth) acrylic acid ester compound having an isocyanate group represented by the following formula (i') is allowed to act on the hydroxy group contained in the hydroxyalkyl group.
  • the (meth) acryloyloxyalkyl group-substituted arylamino compound include the above-mentioned hydroxyalkyl group-substituted arylamino compound obtained by allowing (meth) acrylic acid halide or (meth) glycidyl acrylate to act on the hydroxy group.
  • the ester compound to be used is mentioned.
  • the (meth) acrylic acid halide include (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide.
  • (meth) acrylic acid ester compound having an isocyanate group represented by the above formula (i') include 2-isocyanatoethylacrylate, 2-isocyanatoethyl methacrylate and 1,1- (bis). Acryloyloxymethyl) ethyl isocyanate can be mentioned.
  • 2-isocyanatoethylacryllate is preferable from the viewpoint of a simple synthetic method.
  • triazine ring-containing polymers include those containing repeating units represented by the formulas (21) to (28).
  • R 102 has the same meaning as above.
  • R 102 has the same meaning as above.
  • R 102 has the same meaning as above.
  • R 102 has the same meaning as above.
  • the weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, further improving heat resistance and lowering the shrinkage rate. From this point of view, 2,000 or more is preferable, 50,000 or less is preferable, and 30,000 or less is more preferable, and 25,000 or less is preferable from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution. Even more preferable, 10,000 or less is most preferable.
  • the weight average molecular weight in the present invention is the average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.
  • the triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010/128661 described above. That is, after reacting the trihalogenated triazine compound with the aryldiamino compound in an organic solvent, for example, an arylamino compound having a hydroxyalkyl group (hydroxy-containing group), which is an end-capping agent, or an acryloyloxyalkyl group (acryloyloxyalkyl group).
  • an organic solvent for example, an arylamino compound having a hydroxyalkyl group (hydroxy-containing group), which is an end-capping agent, or an acryloyloxyalkyl group (acryloyloxyalkyl group).
  • the triazine ring of the present invention is contained by reacting with at least one arylamino compound selected from an arylamino compound having an acryloyl-containing group) and an arylamino compound having a group represented by the formula (i) (acryloyl-containing group).
  • a polymer can be obtained.
  • the triazine ring-containing polymer (23) is prepared by reacting the triazine compound (29) and the aryldiamino compound (30) in a suitable organic solvent and then using an end-capping agent. It can be obtained by reacting with at least one arylamino compound (31) selected from an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by the formula (i).
  • X represents a halogen atom independently of each other, and Ra represents a hydroxyalkyl group or a group represented by the formula (i).
  • the triazine ring-containing polymer (27) is end-sealed after reacting the triazine compound (29) and the aryldiamino compound (32) in a suitable organic solvent. It can be obtained by reacting with at least one arylamino compound (31) selected from an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by the formula (i), which is an agent.
  • X represents a halogen atom independently of each other, and Ra represents a hydroxyalkyl group or a group represented by the formula (i).
  • the charging ratio of the aryldiamino compound (30) or (32) is arbitrary as long as the desired polymer can be obtained, but the aryldiamino compound is based on 1 equivalent of the triazine compound (29). (30) or (32) 0.01 to 10 equivalents are preferable, and 0.7 to 5 equivalents are more preferable.
  • the aryldiamino compound (30) or (32) may be added in a neat manner or in a solution dissolved in an organic solvent, but the latter method is considered in consideration of ease of operation and controllability of the reaction. Is preferable.
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is particularly preferably about ⁇ 30 to 150 ° C., more preferably ⁇ 10 to 100 ° C.
  • the triazine ring-containing polymer (23) is an aryl having a hydroxyalkyl group, which is an end-capping agent, after reacting the triazine compound (29) and the aryldiamino compound (30) in a suitable organic solvent. It is reacted with an amino compound (31') to obtain a triazine ring-containing polymer (23') (first step), and then the hydroxy of the hydroxyalkyl group further contained in the triazine ring-containing polymer (23').
  • R a1 represents a hydroxyalkyl group
  • X, A 3 , A 4 , Ra and a represent the same meanings as described above.
  • the triazine ring-containing polymer (27) is an aryl having a hydroxyalkyl group, which is a terminal sealant, after reacting the triazine compound (29) and the aryldiamino compound (32) in a suitable organic solvent. It is reacted with an amino compound (31') to obtain a triazine ring-containing polymer (27') (first step), and then the hydroxy of the hydroxyalkyl group further contained in the triazine ring-containing polymer (27').
  • R a1 represents a hydroxyalkyl group
  • X, A 3 , A 4 , Ra and a represent the same meanings as described above.
  • the charging ratio and addition method of the aryldiamino compound (30) in the first step, and the reaction temperature in the reaction until the triazine ring-containing polymer (23') is obtained are as described in Scheme 1. The same can be done.
  • the charging ratio of the (meth) acrylic acid ester compound having an isocyanate group represented by the formula (i') to the triazine ring-containing polymer (23') is the hydroxyalkyl group and the formula (i). It can be arbitrarily set according to the ratio with the group represented by, and is preferably 0.1 to 10 equivalents, more preferably 0.
  • the charging ratio is 1 equivalent of the arylamino compound having the hydroxyalkyl group used.
  • the above (meth) acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0 to 1.0 to. It is 1.5 equivalents.
  • the reaction temperature in the reaction is the same as the reaction temperature in the reaction for obtaining the triazine ring-containing polymer (23'), but in consideration of preventing the (meth) acryloyl group from polymerizing during the reaction, 30 -80 ° C is preferable, 40-70 ° C is more preferable, and 50-60 ° C is even more preferable.
  • the charging ratio and addition method of the aryldiamino compound (32) in the first step, and the reaction temperature in the reaction until the triazine ring-containing polymer (27') is obtained are the same as those described in Scheme 2. Can be.
  • the charging ratio of the (meth) acrylic acid ester compound having an isocyanate group represented by the formula (i') to the triazine ring-containing polymer (27') is the hydroxyalkyl group and the formula (i). It can be arbitrarily set according to the ratio with the group represented by, and is preferably 0.1 to 10 equivalents, more preferably 0.
  • the charging ratio is 1 equivalent of the arylamino compound having the hydroxyalkyl group used.
  • the above (meth) acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0 to 1.0 to. It is 1.05 equivalent.
  • the reaction temperature in the reaction is the same as the reaction temperature in the reaction for obtaining the triazine ring-containing polymer (27'), but in consideration of preventing the (meth) acryloyl group from polymerizing during the reaction, 30 -80 ° C is preferable, 40-70 ° C is more preferable, and 50-60 ° C is even more preferable.
  • the reaction may be carried out in the presence of a polymerization inhibitor in order to prevent the (meth) acryloyl group from polymerizing during the reaction.
  • a polymerization inhibitor examples include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxylamine or salts thereof, benzoquinones, phenolic polymerization inhibitors, phenothiazines and the like.
  • N-nitrosophenylhydroxylamine or salts thereof are preferable because they are excellent in the polymerization inhibitory effect.
  • N-nitrosophenylhydroxylamine salts include N-nitrosophenylhydroxyamine ammonium salt and N-nitrosophenyl hydroxyamine aluminum salt.
  • benzoquinones include p-benzoquinone and 2-methyl-1,4-benzoquinone.
  • examples of the phenolic polymerization inhibitor include hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol and the like.
  • the amount of the polymerization inhibitor used is not particularly limited, but is, for example, 1 to 200 ppm by mass ratio with respect to the (meth) acrylic acid ester compound having an isocyanate group represented by the formula (i'). It may be 10 to 100 ppm.
  • organic solvent various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran (THF), dioxane, dimethylsulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetra.
  • THF tetrahydrofuran
  • dioxane dimethylsulfoxide
  • N N-dimethylformamide
  • N-methyl-2-pyrrolidone tetra.
  • Methylurea hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N', N'-tetramethylmalonic acid amide, N- Methylcaprolactam, N-acetylpyrrolidin, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methylformamide, N, N'- Examples thereof include amide solvents such as dimethylpropylene urea and mixed solvents thereof.
  • N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable. Is preferable.
  • various bases usually used at the time of polymerization or after polymerization may be added.
  • this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxydo, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, and oxidation.
  • the amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (29). In addition, these bases may be used as an aqueous solution.
  • the product can be easily purified by a reprecipitation method or the like.
  • the amount of the end-capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, relative to 1 equivalent of the halogen atom derived from the surplus triazine compound not used in the polymerization reaction.
  • 0.5 to 2 equivalents are even more preferred.
  • the reaction solvent and the reaction temperature include the same conditions as described in the first step reaction of Scheme 1 or Scheme 2, and the terminal encapsulant is an aryldiamino compound (30) or (32). It may be prepared at the same time.
  • An unsubstituted arylamino compound having no cross-linking group may be used, and terminal encapsulation may be performed with two or more kinds of groups.
  • Examples of the aryl group of this unsubstituted arylamino compound include the same as above.
  • unsubstituted arylamino group examples include those represented by the following formula (33), but the present invention is not limited thereto.
  • the unsubstituted arylamino group can be introduced by using the corresponding unsubstituted arylamino compound in the production method described later.
  • Specific examples of the unsubstituted arylamino compound include aniline and the like.
  • the ratio of the arylamino compound having a cross-linking group and the unsubstituted arylamino compound is such that the cross-linking group is used from the viewpoint of achieving a good balance between solubility in an organic solvent and yellowing resistance.
  • 0.1 to 1.0 mol of the unsubstituted arylamino compound is preferable, 0.1 to 0.5 mol is more preferable, and 0.1 to 0.3 mol is even more preferable.
  • the above-mentioned triazine ring-containing polymer of the present invention can be suitably used as a film-forming composition, and in this case, a cross-linking agent may be added.
  • the cross-linking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the cross-linking group of the above-mentioned triazine ring-containing polymer.
  • Such compounds include melamine compounds having cross-linking substituents such as methylol groups and methoxymethyl groups (eg, phenoplast compounds, aminoplast compounds, etc.), substituted urea compounds, and cross-links such as epoxy groups or oxetane groups.
  • Examples include compounds containing forming substituents (for example, polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing block isocyanate groups, compounds having acid anhydride groups, compounds having (meth) acrylic groups, and the like.
  • compounds containing an epoxy group, a blocked isocyanate group, and a (meth) acrylic group are preferable, and in particular, a compound having a blocked isocyanate group or a photocurable compound can be photocured without using an initiator.
  • Polyfunctional epoxy compounds and / or polyfunctional (meth) acrylic compounds that provide the same composition are preferred. It should be noted that these compounds need only have at least one cross-linking substituent when used for the terminal treatment of the polymer, and at least two cross-linking substituents when used for the cross-linking treatment between the polymers. Must have.
  • the polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples thereof include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol diglycidyl.
  • YH-434 and YH434L manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • Epolide GT-401 which is an epoxy resin having a cyclohexene oxide structure
  • the polyfunctional (meth) acrylic compound is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule. Specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethyl propantriacrylate, and ethoxylated Trimethylol propantrimethacrylate, glycerin triacrylate ethoxylated, glycerin trimethacrylate ethoxylated, pentaerythritol tetraacrylate ethoxylated, pentaerythritol tetramethacrylate ethoxylated, dipentaerythritol hexaacrylate ethoxylated, polyglycerin monoethylene oxide polyacrylate, polyglycerin Polyethylene glycol
  • the polyfunctional (meth) acrylic compound is available as a commercially available product, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, and A-. 9300 (Tris isocyanurate (2-acryloyloxyethyl)), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 14G 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, APG-100, APG-200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.),
  • the above-mentioned polybasic acid-modified acrylic oligomer is also available as a commercially available product, and specific examples thereof include Aronix M-510, 520 (all manufactured by Toagosei Co., Ltd.) and the like.
  • the compound having an acid anhydride group is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid, and specific examples thereof include phthalic anhydride and tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl anhydride, succinic anhydride, dodecenyl anhydride, etc.
  • an isocyanate group (-NCO) has two or more blocked isocyanate groups in one molecule blocked by an appropriate protective group and is exposed to a high temperature during thermal curing, Especially limited as long as the protective group (block portion) is thermally dissociated and detached, and the generated isocyanate group causes a cross-linking reaction with the cross-linking group (for example, hydroxy-containing group) of the triazine ring-containing polymer of the present invention.
  • the cross-linking group for example, hydroxy-containing group
  • examples thereof include compounds having two or more groups represented by the following formulas in one molecule (these groups may be the same or different from each other).
  • R b represents an organic group in the block portion.
  • Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.
  • the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis (4-cyclohexamethylene diisocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimer thereof. , Trimers, and reactants of these with diols, triols, diamines, or triamines.
  • the blocking agent examples include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitrophenol. , P-Chlorophenol, o-, m- or p-cresol and other phenols; ⁇ -caprolactam and other lactams, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes.
  • Classes; pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol.
  • Compounds containing a blocked isocyanate group are also available as commercial products, and specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, and B-874N. B-882N, B-7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Kagaku Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, same MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Co., Ltd.), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), TRIXENE (registered trademark) BI-7950, BI-7951, Examples thereof include BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, BI-7992 (manufactured by Ba
  • the aminoplast compound is not particularly limited as long as it has two or more methoxymethyl groups in one molecule, and is not particularly limited.
  • hexamethoxymethylmelamine CYMEL registered trademark
  • tetrabutoxymethylglycoluryl 1170 tetrabutoxymethylglycoluryl 1170.
  • Tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nippon Cytec Industries Co., Ltd.), etc., Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, which is a methylated melamine resin, Examples thereof include MX-750LM, MX-270, which is a methylated urea resin, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.) and other melamine compounds such as the Nicarac series.
  • the polyfunctional oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. For example, OXT-221, OX-SQ-H, and OX-SC containing an oxetane group. (The above is manufactured by Toagosei Co., Ltd.) and the like.
  • the phenoplast compound has two or more hydroxymethyl groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes a dehydration condensation reaction with the crosslinking group of the triazine ring-containing polymer of the present invention.
  • the cross-linking reaction proceeds.
  • the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, and the like.
  • the phenoplast compound is also available as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, and BI25X-DF. , BI25X-TPA (all manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like.
  • a polyfunctional (meth) acrylic compound is preferable because it can suppress a decrease in the refractive index due to the addition of a cross-linking agent and the curing reaction proceeds rapidly.
  • a triazine ring-containing polymer A polyfunctional (meth) acrylic compound having the following isocyanuric acid skeleton is more preferable because of its excellent compatibility.
  • the polyfunctional (meth) acrylic compound having such a skeleton include NK ester A-9300 and A-9300-1CL (both manufactured by Shin Nakamura Chemical Industry Co., Ltd.).
  • R 111 to R 113 are monovalent organic groups having at least one (meth) acrylic group at the end, independent of each other.
  • a polyfunctional (meth) acrylic compound (hereinafter referred to as a low-viscosity cross-linking agent) of 1 to 3,000 mPa ⁇ s, more preferably 1 to 1,000 mPa ⁇ s, even more preferably 1 to 500 mPa ⁇ s, alone or. It is preferable to use in combination of two or more kinds, or in combination with the above-mentioned polyfunctional (meth) acrylic compound having an isocyanuric acid skeleton.
  • Such a low-viscosity cross-linking agent is also available as a commercially available product.
  • polyfunctional (meth) acrylic compounds NK ester A-GLY-3E (85 mPa ⁇ s, 25 ° C.), A-GLY.
  • NK ester A-GLY-20E manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • ATM-35E manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • the above-mentioned polyfunctional (meth) acrylic compound having an isocyanuric acid skeleton are preferably used in combination.
  • a thin film made of the triazine ring-containing polymer of the present invention is laminated on a protective film such as PET or a polyolefin film and light is irradiated through the protective film, the thin film laminated film also cures well without being affected by oxygen. You can get sex.
  • the protective film needs to be peeled off after curing, it is preferable to use a polybasic acid-modified acrylic oligomer that gives a thin film having good peelability.
  • the above-mentioned cross-linking agent may be used alone or in combination of two or more.
  • the amount of the cross-linking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but the lower limit thereof is preferably 2 parts by mass, more preferably 5 parts by mass in consideration of solvent resistance. Further, in consideration of controlling the refractive index, the upper limit thereof is preferably 20 parts by mass, more preferably 15 parts by mass.
  • composition of the present invention may also contain an initiator corresponding to each cross-linking agent.
  • an initiator corresponding to each cross-linking agent.
  • photocuring proceeds to give a cured film without using an initiator.
  • Initiators may be used in some cases.
  • a photoacid generator or a photobase generator can be used.
  • the photoacid generator a known one may be appropriately selected and used.
  • an onium salt derivative such as a diazonium salt, a sulfonium salt or an iodonium salt can be used.
  • aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate and di (4-methylphenyl).
  • Diaryliodonium salts such as iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenylsulfide-bishexafluoroantimonate, 4,4'-bis (diphenylsulfoni) E) Phenylsulfide-bishexafluorophosphate, 4,4'-bis [di ( ⁇ -hydroxyethoxy) phenylsul
  • onium salts Commercially available products may be used as these onium salts, and specific examples thereof include Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-. L150, SI-L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide) CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by Sun Appro Co., Ltd.), Adecaca Ptomer SP-150, SP-151, SP-170, SP-171 (manufactured by Sun Appro Co., Ltd.) Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2369, CI-2064
  • the photobase generator may be appropriately selected from known ones and used, for example, a Co-amine complex type, an oxime carboxylic acid ester type, a carbamic acid ester type, a quaternary ammonium salt type photobase generator and the like.
  • a Co-amine complex type for example, an oxime carboxylic acid ester type, a carbamic acid ester type, a quaternary ammonium salt type photobase generator and the like.
  • a photoacid or a base generator When a photoacid or a base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound. If necessary, the epoxy resin curing agent may be added in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.
  • a photoradical polymerization initiator when a polyfunctional (meth) acrylic compound is used, a photoradical polymerization initiator can be used.
  • the photoradical polymerization initiator may also be appropriately selected from known ones and used, for example, acetophenones, benzophenones, Michler's benzoylbenzoate, amyroxime esters, oxime esters, tetramethylthium monosulfide, thioxanthones and the like. Can be mentioned.
  • a photocleavable photoradical polymerization initiator is preferable.
  • the photocleavable photoradical polymerization initiator is described in the latest UV curing technology (page 159, publisher: Kazuhiro Takausu, publisher: Technical Information Association, 1991).
  • Examples of commercially available photoradical polymerization initiators include BASF's trade names: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850. , CG24-61, OXE01, OXE02, DaroCure 1116, 1173, MBF, BASF Product Name: Lucillin TPO, UCB Product Name: Yubekrill P36, Flateturi Lamberti Product Name: EzaCure KIP150, KIP65LT, KIP100F Examples thereof include KT37, KT55, KTO46, and KIP75 / B.
  • a photoradical polymerization initiator When a photoradical polymerization initiator is used, it is preferably used in the range of 0.1 to 200 parts by mass, preferably in the range of 1 to 150 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. Is more preferable.
  • a polyfunctional thiol compound having two or more mercapto groups in the molecule may be added to the composition of the present invention for the purpose of accelerating the reaction between the triazine ring-containing polymer and the cross-linking agent.
  • a polyfunctional thiol compound represented by the following formula is preferable.
  • the above L represents a divalent to tetravalent organic group, preferably an aliphatic group having 2 to 4 valences of 2 to 12 carbon atoms or a heterocyclic group containing 2 to 4 valences, and 2 to 4 valent carbon atoms. More preferably, it is a trivalent group having up to 8 aliphatic groups or an isocyanuric acid skeleton (1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ring) represented by the following formula. ..
  • the above n represents an integer of 2 to 4 corresponding to the valence of L.
  • Specific compounds include 1,4-bis (3-mercaptobutylyloxy) butane and 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4. , 6- (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane ethanetris (3-mercaptobutyrate), etc. Be done.
  • polyfunctional thiol compounds can also be obtained as commercial products, and examples thereof include Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (all manufactured by Showa Denko KK). These polyfunctional thiol compounds may be used alone or in combination of two or more.
  • the amount to be added is not particularly limited as long as it does not adversely affect the obtained thin film, but in the present invention, 0.01 to 10% by mass in 100% by mass of solid content. % Is preferable, and 0.03 to 6% by mass is more preferable.
  • solvents include water, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, and ethylene.
  • Glycol monoethyl ether ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-Butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glyco
  • glycols such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate Ester solvent;
  • Ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, acetic acid Since it dissolves well in ester solvents such as normal propyl, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate, it is particularly suitable
  • the solid content concentration in the composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness.
  • the solid content concentration is preferably 0.1 to 50% by mass, more preferably 0.1 to 40% by mass.
  • composition of the present invention addition of other components other than the triazine ring-containing polymer, the cross-linking agent and the solvent, for example, a leveling agent, a surfactant, a silane coupling agent, etc., as long as the effects of the present invention are not impaired.
  • the agent may be included.
  • the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol.
  • Polyoxyethylene alkylallyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate
  • sorbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
  • Nonionic surfactants such as sorbitan fatty acid esters, trade names Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd. (formerly manufactured by Gemco Co., Ltd.)), trade names Megafuck F171, F173, R- 08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name Fluorine-based surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), Organosiloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), BYK -302, BYK-307, B
  • surfactants may be used alone or in combination of two or more.
  • the amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferable.
  • the film-forming composition of the present invention can be applied to a substrate, and then heated if necessary to evaporate the solvent, and then heated or irradiated with light to obtain a desired cured film.
  • the coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, inkjet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer.
  • a printing method, a brush coating method, a blade coating method, an air knife coating method, or the like can be adopted.
  • the base material silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, metal nanowires, polyethylene terephthalate (PET), plastic, glass, etc.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • PET polyethylene terephthalate
  • the firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at, for example, 110 to 400 ° C.
  • the firing method is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an atmosphere, an inert gas such as nitrogen, or an appropriate atmosphere such as in a vacuum.
  • conditions suitable for the process process of the target electronic device may be selected, and firing conditions may be selected so that the physical property values of the obtained film match the required characteristics of the electronic device.
  • the conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the cross-linking agent used.
  • the thin film transistor and the cured film of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage, liquid crystal displays, organic EL elements (organic EL displays and organic EL illuminations), A member for manufacturing touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure devices, etc. It can be suitably used in the fields of electronic devices and optical materials.
  • LED optical semiconductor
  • TFTs organic thin film transistors
  • the thin film or cured film produced from the composition of the present invention has high transparency and high refractive index, and therefore, when used as a flattening film or a light scattering layer for organic EL illumination, its light extraction efficiency ( Light diffusion efficiency) can be improved, and its durability can be improved.
  • composition of the present invention is used for the light scattering layer of organic EL illumination
  • a known light diffusing agent can be used as the light diffusing agent, and the present invention is not particularly limited. These may be used alone, in combination of two or more of the same type, or in combination of two or more of different types.
  • Examples of the light diffusing agent include organic light diffusing agents.
  • Examples of the organic light diffusing agent include crosslinked polymethylmethacrylate (PMMA) particles, crosslinked polymethylacrylate particles, crosslinked polystyrene particles, crosslinked styrene-acrylic copolymer particles, melamine-formaldehyde particles, silicone resin particles, silica-acrylic composite particles, and nylon particles. , Benzoguanamine-formaldehyde particles, benzoguanamine / melamine / formaldehyde particles, fluororesin particles, epoxy resin particles, polyphenylene sulfide resin particles, polyether sulfone resin particles, polyacrylonitrile particles, polyurethane particles and the like.
  • PMMA polymethylmethacrylate
  • PMMA polymethylmethacrylate
  • crosslinked polystyrene particles crosslinked polystyrene-acrylic copolymer particles
  • melamine-formaldehyde particles silicone resin particles
  • 1,3-phenylenediamine [2] 35.18 g, 0.325 mol, manufactured by Amino-Chem
  • DMAc dimethylacetamide
  • 1,3-phenylenediamine [2] was dissolved in DMAc by stirring. Then, it was cooled to -10 ° C by an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (60.0 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the measurement result of 1 H-NMR spectrum of compound P-1 is shown in FIG.
  • the weight average molecular weight Mw of compound P-1 measured by GPC in terms of polystyrene was 6,070, and the polydispersity Mw / Mn was 2.6.
  • 1,3-phenylenediamine [2] (11.73 g, 0.108 mol, manufactured by Amino-Chem) and 204.96 g of dimethylacetamide (DMAc, manufactured by Kanto Chemical Co., Ltd.) were added. After substitution with nitrogen, 1,3-phenylenediamine [2] was dissolved in DMAc by stirring. Then, it was cooled to -10 ° C by an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (20.00 g, 0.108 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). Was added while confirming that the internal temperature did not exceed 0 ° C.
  • aniline [6] (10.10 g, 0.108 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2- (4-aminophenyl) ethanol [3] (104.14 g, 0.759 mol, manufactured by Sugai Chemical Industry Co., Ltd., was previously dissolved in 208.29 g of DMAc, added dropwise, and the mixture was stirred for 3 hours.
  • acrylic acid chloride 14.72 g, 0.163 mol, manufactured by Tokyo Chemical Industry Co., Ltd. was added dropwise, and the mixture was further stirred for 30 minutes.
  • the recovered organic layer was added dropwise to a mixed solution of methanol (251 g) and ion-exchanged water (629 g), and the mixture was reprecipitated.
  • the obtained precipitate was filtered off and dried in a vacuum drier at 120 ° C. for 8 hours to obtain 31.0 g of the target polymer compound [7] (hereinafter referred to as P-3).
  • the measurement result of 1 H-NMR spectrum of compound P-3 is shown in FIG.
  • the weight average molecular weight Mw of compound P-3 measured by GPC in terms of polystyrene was 7,270, and the polydispersity Mw / Mn was 3.3.
  • the measurement result of 1 H-NMR spectrum of compound P-4 is shown in FIG.
  • the weight average molecular weight Mw of compound P-4 measured by GPC in terms of polystyrene was 11,580, and the polydispersity Mw / Mn was 3.7.
  • the measurement results of the 1 H-NMR spectrum of compound P-5 are shown in FIG.
  • the weight average molecular weight Mw of compound P-5 measured by GPC in terms of polystyrene was 6,182, and the polydispersity Mw / Mn was 5.8.
  • 1,3-phenylenediamine [2] (42.22 g, 0.390 mol, manufactured by Amino-Chem) and 672.62 g of dimethylacetamide (DMAc, manufactured by Kanto Chemical Co., Ltd.).
  • DMAc dimethylacetamide
  • 1,3-phenylenediamine [2] was dissolved in DMAc by stirring. Then, it was cooled to -10 ° C by an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (60.00 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.).
  • 2-aminoethanol (59.62 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, the temperature was lowered to room temperature, stirring was performed for 30 minutes, and then stirring was stopped.
  • THF (369 g), ammonium acetate (415 g) and ion-exchanged water (415 g) were added to the reaction solution, and the mixture was stirred for 30 minutes.
  • the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered.
  • the recovered organic layer was added dropwise to a mixed solution of methanol (461 g) and ion-exchanged water (1,845 g), and the mixture was reprecipitated.
  • the obtained precipitate was filtered off and dried in a vacuum drier at 120 ° C. for 8 hours to obtain 89.3 g of the target polymer compound [10] (hereinafter referred to as P-6).
  • the measurement results of the 1 H-NMR spectrum of compound P-6 are shown in FIG.
  • the weight average molecular weight Mw of compound P-6 measured by GPC in terms of polystyrene was 23,350, and the polydispersity Mw / Mn was 6.5.
  • Example 2-1 Preparation of cross-linking agent-added film-forming composition and preparation of cured film
  • P-1 (2.40 g) obtained in Example 1-1 was dissolved in cyclopentanone (hereinafter abbreviated as CPN) (5.60 g), and ATM-35E (30% by mass CPN solution) was used as a cross-linking agent.
  • CPN cyclopentanone
  • ATM-35E (30% by mass CPN solution
  • This SP-1 solution was spin-coated on a 50 mm ⁇ 50 mm ⁇ 0.7 t non-alkali glass substrate with a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, and then spin-coated at 100 ° C. for 1 minute using a hot plate. After the temporary drying, a cured film (hereinafter referred to as SP-1 film) was obtained by irradiating an exposure amount of 400 mJ / cm 2 with light having a wavelength of 365 nm with a UV irradiation device.
  • Example 2-2 P-2 (1.20 g) obtained in Example 1-2 was dissolved in CPN (2.80 g), and ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) in a 50 mass% CPN solution as a cross-linking agent was used.
  • Example 2-3 ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) in which P-3 (2.40 g) obtained in Example 1-3 is dissolved in CPN (5.60 g) and a 30 mass% CPN solution is used as a cross-linking agent.
  • Residual film ratio (%) (film thickness after solvent exposure) ⁇ (film thickness before solvent exposure) x 100
  • the transmittance was also measured before the solvent was exposed.
  • the results of the refractive index, film thickness measurement, residual film ratio and average transmittance at 300 to 800 nm are shown in Table 1, and the photomicrographs of the cured film surface of Examples 2-1 to 2-3 are shown in FIGS. 7 to 9 for comparative examples. Micrographs of the surface of the cured film of 2-1 to 2-2 are shown in FIGS. 10 to 11, respectively.
  • the cured films (SP-1 to SP-3 films) of Examples 2-1 to 2-3 have a high residual film ratio, and as shown in FIGS. 7 to 9, no film roughness or cracks have occurred. Is confirmed, and it can be seen that the solvent resistance (crack resistance) is excellent.
  • the cured film (SP-4 film) of Comparative Example 2-1 was exposed to a solvent and then dried at 120 ° C. for 10 seconds using a hot plate, and then film roughness and cracks occurred (see FIG. 10). The refractive index and film thickness could not be measured.
  • the cured film (SP-5 film) of Comparative Example 2-2 had no film roughness or cracks, but the transmittance was lower than that of Examples (see FIG. 11). From these results, it can be seen that the cured film prepared from the polymer compound obtained in the examples is excellent in solvent resistance (crack resistance) and optical properties because it has a crosslinked site at the polymer terminal. ..
  • aniline [14] (73.39 g, 0.456 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2- (4-aminophenyl) ethanol [13] (62.49 g, 0.456 mol (manufactured by Oakwood) was previously dissolved in 124.97 g of DMAc, added dropwise, and the mixture was stirred for 3 hours. Then, the temperature was lowered to room temperature, n-propylamine (115.39 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 30 minutes and then the stirring was stopped.
  • the measurement result of 1 H-NMR spectrum of compound P-11 is shown in FIG.
  • the weight average molecular weight Mw of compound P-11 measured by GPC in terms of polystyrene was 6,070, and the polydispersity Mw / Mn was 2.6.
  • the measurement result of 1 H-NMR spectrum of compound P-13 is shown in FIG.
  • the weight average molecular weight Mw of compound P-13 measured by GPC in terms of polystyrene was 11,580, and the polydispersity Mw / Mn was 3.7.
  • Example 4-1 P-11 (2.50 g) obtained in Example 3-1 was dissolved in PGME (5.83 g), and blocked isocyanate (BI9792, 1,500 mPa ⁇ s, BAXENDEN) in a 70 mass% PGME solution as a cross-linking agent. 0.71 g, 0.25 g of Megafuck F-563 (manufactured by DIC Co., Ltd.) in a 1 mass% PGMEA solution as a surfactant, 0.71 g of PGME, and 1.70 g of THFA (tetrahydrofurfuryl alcohol) are added.
  • PGME 5.83 g
  • blocked isocyanate BI9792, 1,500 mPa ⁇ s, BAXENDEN
  • SP-11 solution a varnish having a solid content of 30% by mass was prepared (hereinafter referred to as SP-11 solution).
  • This SP-11 solution was spin-coated on a 50 mm ⁇ 50 mm ⁇ 0.7 t non-alkali glass substrate with a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, and then spin-coated at 100 ° C. for 1 minute using a hot plate. After the temporary drying, the film was fired at 200 ° C. for 5 minutes to obtain a cured film (hereinafter referred to as SP-11 film).
  • P-1 [4] (29.20 g) obtained in Example 1-1 and 174.84 g of cyclopentanone (CPN, manufactured by Nippon Zeon Corporation) were added to a 500 mL four-necked flask and substituted with nitrogen. After that, it was stirred and dissolved. Then, the solution was heated until the internal temperature reached 60 ° C., 14.51 g of 2-isocyanatoethylacryllate [101] (AOI-VM, manufactured by Showa Denko KK) was added dropwise, and the internal temperature was 60 ° C. The mixture was stirred at ⁇ 5 ° C. for 1 hour to prepare a CPN solution containing 30% by mass of the polymer compound [102] (hereinafter referred to as P-21 solution).
  • CPN 2-isocyanatoethylacryllate
  • 1,3-phenylenediamine [2] (43.98 g, 0.407 mol, manufactured by Amino-Chem), 2,2'-bis (trifluoromethyl) -4,4'- Diamine diphenyl ether [103] (136.75 g, 0.407 mol, manufactured by Wuhan Sunshine) and dimethylacetamide 1949.90 g (DMAc, manufactured by Kanto Kagaku Co., Ltd.) were added, substituted with nitrogen, and then stirred for 1,3.
  • DMAc dimethylacetamide 1949.90 g
  • Tetrahydrofuran (THF, 1456 g), ammonium acetate (1,311 g) and ion-exchanged water (1311 g) were added to the reaction solution, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to methanol (1,748 g) and ion-exchanged water (4,369 g) for reprecipitation. The obtained precipitate was filtered off and dried in a vacuum drier at 150 ° C. for 8 hours to obtain 353.6 g of the target polymer compound [104] (hereinafter referred to as P-22).
  • the weight average molecular weight Mw of compound P-22 measured by GPC in terms of polystyrene was 8,083, and the polydispersity Mw / Mn was 3.2.
  • the measurement result of 1 H-NMR spectrum of compound P-22 is shown in FIG.
  • P-22 polymer compound [104] (30.00 g) and cyclopentanone 93.60 g (CPN, manufactured by Nippon Zeon Corporation) obtained in Example 5-2 were placed in a 300 mL four-necked flask. In addition, after substitution with nitrogen, the mixture was stirred and dissolved. Then, the solution was heated until the internal temperature reached 60 ° C., 10.11 g of 2-isocyanatoethylacrylate (AOI-VM, manufactured by Showa Denko KK) was added dropwise, and the internal temperature was 60 ° C. ⁇ 5 ° C. To prepare a CPN solution containing 30% by mass of the polymer compound [105] (hereinafter referred to as P-23 solution).
  • AOI-VM 2-isocyanatoethylacrylate
  • Example 6-1 P-21 solution (4.42 g) obtained in Example 5-1 and ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 0.088 g as a cross-linking agent, DN-0075 (Nippon Kayaku Co., Ltd.) (Made) 0.088 g, Omnirad 2959 (manufactured by IGM Resins VV) as a photoradical polymerization initiator, 0.053 g, and Megafuck R-40 (manufactured by DIC Co., Ltd.) in a 10 mass% CPN solution as a surfactant.
  • ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • DN-0075 Nippon Kayaku Co., Ltd.
  • Omnirad 2959 manufactured by IGM Resins VV
  • Megafuck R-40 manufactured by DIC Co., Ltd.
  • SP-21 solution a varnish having a solid content of 20% by mass was prepared (hereinafter referred to as SP-21 solution).
  • This SP-21 solution is spin-coated on a 50 mm ⁇ 50 mm ⁇ 0.7 t non-alkali glass substrate with a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, and then spin-coated at 80 ° C. for 3 minutes using a hot plate.
  • a cured film (hereinafter referred to as SP-21 film) was obtained by irradiating an exposure amount of 200 mJ / cm 2 with light having a wavelength of 365 nm with a UV irradiation device.
  • Solvent resistance (crack resistance) and transmittance measurement The substrate with the cured film prepared above was set on a spin coater, and 1 ml of CPN was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds so that the liquid did not scatter from the substrate. Then, the solvent was removed from the substrate by rotating at 1,000 rpm for 30 seconds. Finally, after drying at 80 ° C.
  • Residual film ratio (%) (film thickness after solvent exposure) ⁇ (film thickness before solvent exposure) x 100
  • the transmittance was also measured before the solvent was exposed.
  • Table 3 The results of the refractive index, film thickness measurement, residual film ratio and average transmittance at 300 to 800 nm are shown in Table 3, and the photomicrograph of the surface of the cured film of Example 6-1 is shown in FIG.
  • Example 6-2 P-23 solution (13.27 g) obtained in Example 5-3, ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 0.20 g as a cross-linking agent, DN-0075 (Nippon Kayaku Co., Ltd.) (Manufactured by) 0.20 g, Omnirad 2959 (manufactured by IGM Resins VV) as a photoradical polymerization initiator, 0.12 g, and Megafuck R-40 (manufactured by DIC Co., Ltd.) in a 10 mass% CPN solution as a surfactant.
  • ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • DN-0075 Nippon Kayaku Co., Ltd.
  • Omnirad 2959 manufactured by IGM Resins VV
  • Megafuck R-40 manufactured by DIC Co., Ltd.
  • SP-22 solution a varnish having a solid content of 15% by mass was prepared (hereinafter referred to as SP-22 solution).
  • This SP-22 solution was spin-coated on a 50 mm ⁇ 50 mm ⁇ 0.7 t non-alkali glass substrate with a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, and then spin-coated at 80 ° C. for 3 minutes using a hot plate.
  • a cured film (hereinafter referred to as SP-22 film) was obtained by irradiating an exposure amount of 200 mJ / cm 2 with light having a wavelength of 365 nm with a UV irradiation device.
  • Solvent resistance (crack resistance) and transmittance measurement The substrate with the cured film prepared above was set on a spin coater, and 1 ml of CPN was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds so that the liquid did not scatter from the substrate. Then, the solvent was removed from the substrate by rotating at 1,000 rpm for 30 seconds. Finally, after drying at 80 ° C.
  • Residual film ratio (%) (film thickness after solvent exposure) ⁇ (film thickness before solvent exposure) x 100
  • the transmittance was also measured before the solvent was exposed.
  • Table 4 The results of the refractive index, film thickness measurement, residual film ratio and average transmittance at 300 to 800 nm are shown in Table 4, and the photomicrograph of the surface of the cured film of Example 6-2 is shown in FIG.

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Abstract

L'invention concerne un polymère contenant un cycle triazine qui contient une structure d'unité de répétition telle que, par exemple, la structure représentée par la formule (24). (Dans la formule, R102 représente un groupe de réticulation).
PCT/JP2020/039866 2019-10-25 2020-10-23 Polymère contenant un cycle triazine et composition filmogène le contenant WO2021079977A1 (fr)

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US17/770,373 US20230002555A1 (en) 2019-10-25 2020-10-23 Triazine ring-containing polymer and film forming composition containing same
KR1020227016366A KR20220095196A (ko) 2019-10-25 2020-10-23 트리아진환 함유 중합체 및 그것을 포함하는 막 형성용 조성물
EP20878509.7A EP4050049A4 (fr) 2019-10-25 2020-10-23 Polymère contenant un cycle triazine et composition filmogène le contenant
CN202080074297.XA CN114599704A (zh) 2019-10-25 2020-10-23 含三嗪环的聚合物及含有该聚合物的膜形成用组合物
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WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique
WO2022225001A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Polymère à teneur en cycle triazine, et composition pour formation de motif
WO2022225002A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Polymère à teneur en cycle triazine, et composition pour formation de film contenant celui-ci

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WO2022210095A1 (fr) * 2021-04-02 2022-10-06 Jsr株式会社 Polymère, composition, produit durci, corps multicouche et composant électronique
WO2022225001A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Polymère à teneur en cycle triazine, et composition pour formation de motif
WO2022225002A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Polymère à teneur en cycle triazine, et composition pour formation de film contenant celui-ci

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